Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Kerosene composition
The present invention relates to kerosene
compositions, particularly for heating purposes.
Kerosene is widely used for heating purposes and
cooking purposes. When conventional kerosene is used for
heating purposes there is an oily smell when the kerosene
is being handled when supplying the oil, for example, and
the user is subjected to an unpleasant sensation.
Furthermore, incomplete combustion occurs on ignition and
on extinguishing when this type of kerosene is used in an
open-type stove such as a portable stove or a fan heater
or when it is used in a small portable cooking stove in
the kitchen, and there is a problem in that there is an
unpleasant smell due to the unburned hydrocarbons which
are produced at this time.
On the other hand, the demand for higher levels of
safety and comfort (the production of smaller amounts of
NOx, hydrocarbon compounds, CO, 502, etc. and no
accompanying unpleasant smell) by the user in connection
with oil stoves has increased year by year. Furthermore,
in recent years kerosene which has been stored through
the summer has been recirculated and problems also arise
in that oil stoves break down as a result of using such
kerosene. There is thus also a demand for improvement of
the storage stability of kerosene. In view of such a
situation, the kerosene which is being used in oil stoves
must respond satisfactorily to these user demands.
A method in which a kerosene vaporisation catalyst
is used, described in JP-B-59-16819, a method in which a
deodorising agent is added to the kerosene, described in
JP-B-54-32003, and a kerosene comprising n-paraffins and
iso-paraffins, described in JP-A-63-150380, for example,
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have been suggested as methods for overcoming the
generally observed problems of the unpleasant sensation
when handling kerosene and the unpleasant smell when
kerosene is being ignited or extinguished.
However, with the method in which a kerosene
vaporisation catalyst is used, the catalyst deteriorates
with the passage of time and so it has been difficult to
maintain clean combustion over a prolonged period of
time. Furthermore, the method in which a deodorising
agent is added to kerosene is not very effective because
of the problem that the smell is not agreeable to some
people. Furthermore, although kerosenes comprising
n-paraffins and iso-paraffins do not have an unpleasant
smell when they are being handled, when they are ignited
or when they are extinguished, and the exhaust gas is
also clean, the production costs are greatly increased
and there is a problem in that kerosene of this type is
inevitably expensive. Furthermore, kerosenes comprising
iso-paraffins and n-paraffins which have 9 or 10 carbon
atoms as the main component have a lower density than
existingl,~kerosenes and the fuel consumption by volume~is
increased, and so, for example, there is a risk that the
JIS specification (of the Japanese Standards Association)
for the indicated fuel consumption of an oil stove will
not be satisfied. Moreover, the flash point is reduced
and there are problems with safety in respect, for
example, of the extinguishing time.
The present invention provides kerosene compositions
of which the extinguishing time and the amount of heat
generated [hereinafter, the amount of heat generated or
the heating performance, in the absence of any indication
to the contrary, signifies the amount of heat generated
with respect to time {J/h)] are about the same as those
of kerosenes in general, with which the kerosene itself
has very little smell and has no unpleasant smell when it
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is being handled, with which there is no smell when the
kerosene is ignited and when it is extinguished, which
has good combustion properties, with which the exhaust
gas on burning is clean, and which has excellent storage
stability, a short extinguishing time and excellent
heating performance, features which have not been
obtained with the conventional methods.
As a result of carrying out thorough research with a
view to resolving the aforementioned problems associated
with the prior art, it has been found that the
aforementioned advantages can be realised with a kerosene
which has n-paraffins and iso-paraffins as the main
components, which has specified distillation properties
and which has a specified composition instead of a
conventional kerosene which has been obtained by the
distillation of crude oil.
According to the present invention there is provided
a kerosene composition comprising, in relation to the
total composition, at least 99% by weight of n-paraffins
and iso-paraffins, which composition has the properties
indicated by the following formulae:
(A) 6.0°C <_ FBP (end point) - 95o distillation point <_
11. 0°C
(B) 240°C <_ FBP <_ 270°C
(C) 150°C <_ IBP (initial distillation point) <_ 165°C.
Preferably, said kerosene composition comprises a
Cg_12 paraffin mixture of Cg-12 n-paraffins and Cg_12
iso-paraffins, and C13-16 iso-paraffins.
Preferably, in said kerosene composition the mixing
ratio of the Cg_12 paraffin mixture consisting of Cg_12
n-paraffins and Cg_12 iso-paraffins, to the C13-16
iso-paraffins, as proportions by weight, is from 80:20 to
40:60, more preferably 70:30 to 50:50.
Most preferably, in said kerosene composition, the
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n-paraffins and/or iso-paraffins have been obtained by
means of Fischer-Tropsch synthesis.
The present invention will be described in more
detail below.
The kerosene compositions of the present invention
can be obtained by taking synthesis gas obtained by the
partial oxidation, steam reforming, etc. of natural gas
or coal, for example, forming a long chain alkyl
hydrocarbon polymer oil by means of a Fischer-Tropsch
reaction and then carrying out hydrocracking and
distillation to prepare a material with the prescribed
properties. Furthermore, they can be obtained by
cracking or synthesis, for example, from the various
fractions which are obtained in petroleum refining.
Kerosene compositions are mixtures of various types
of compound, and it is very difficult to predict general
properties from a simple distillation curve or the
properties of the individual compounds but, as a result
of thorough research, it has been found that the aims can
be achieved by ensuring that the properties of a kerosene
composition, which has n-paraffins and iso-paraffins as
the main components and which has an excellent
extinguishing time and amount of heat generated, satisfy
the aforementioned conditions (A) to (C).
If, in the present invention, the component
comprising n-paraffins and iso-paraffins is less than 990
by weight of the whole, then an aromatic component, an
olefinic component or an oxygen-containing component, for
example, is present and, depending on the particular
case, components such as nitrogen components and sulphur
components are present, and there may be a sensation of
smell when the kerosene is being handled, when it is
ignited and when it is extinguished, and the storage
stability may become similar to that of general kerosene.
The aforementioned conditions (A) to (C) are
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essential for providing a kerosene composition with
excellent heating performance and a short extinguishing
time. By including a "heavy fraction" and especially
C13-16 iso-paraffins, which satisfy the specifications
(A) to (C), the evaporation of a low boiling point
fraction is suppressed and it also has the effect of
shortening the extinguishing time. On the other hand, if
there is too much "heavy fraction", then the surface
tension increases above the requirement and the fuel is
taken up by the stove wick only with difficulty and there
is likely to be reduction in heating capacity. Moreover,
with n-paraffins and iso-paraffins accounting for at
least 99% by weight of the whole of the kerosene
composition, there is no unpleasant smell due to an
aromatic component, for example, the exhaust gas is
clean, and it also has the effect of providing good
storage stability.
Furthermore, the extinguishing time is even shorter
if material with an FBP (end point) of 250°C or above is
used.
If in the present invention the number of carbon
atoms of the paraffins is 7 or less then the flash point
is too low and it is possible that the specification for
flash point of at least 40°C for kerosene as laid down in
JIS K 2203 will not be met, and if the number of carbon
atoms of the n-paraffins exceeds 12 then the low
temperature fluidity becomes poor and this is
undesirable. Moreover, if the number of carbon atoms of
the iso-paraffins exceeds 16 then it is possible that the
requirement that the 95% distillation point is not more
than 270°C laid down in JIS K2203 will not be met and
this is undesirable. Moreover, if the proportion of the
Cg_12 carbon atom paraffin mixture is too great then the
extinguishing time is longer and an excess of fuel is
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supplied in a wick-type stove and the amount of heat
generated is increased and this in undesirable on safety
grounds. Furthermore, if there is too much C13-16
iso-paraffin then, conversely, the supply of fuel in a
wick-type stove is inadequate, the amount of heat which
is generated is reduced and satisfactory heating
performance is not obtained.
Moreover, the Cg_12 n-paraffins and the Cg-12
iso-paraffins in the present invention can be constituted
with an optional mixing ratio. This is because, provided
that they are paraffins which have a number of carbon
atoms within this range, in the present invention both
the normal and iso-paraffins can be regarded as having
roughly the same properties.
If the n-paraffin content exceeds 800, it meets the
JIS specification but the extinguishing time becomes a
little longer than that of a commercial kerosene and this
is undesirable. Moreover, the fuel supply in a wick-type
stove becomes excessive, the amount of heat generated is
increased and this is undesirable on safety grounds.
Examples of the n-paraffins which can be used in the
present invention include n-nonane, n-decane, n-undecane
and n-dodecane, and examples of the iso-paraffins which
can be used include n-methylundecane,
2,2-dimethylundecane, 2-methyldodecane,
2,2-dimethyldodecane, 2-methyltridecane,
2,2-dimethyltridecane and 2-methyltetradecane.
The kerosene compositions of the present invention
have the properties (1) to (4) indicated below, and they
have a high smoke point and excellent combustion
properties. If the smoke point is high and the
combustion properties are improved, the time taken to
achieve complete combustion after ignition is shortened
and complete combustion is promoted at the time of normal
combustion. Consequently there is no unpleasant smell or
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soot on ignition and the exhaust gas during ignition and
during normal combustion is also clean.
(1) Flash Point: At least 40°C
(2) Sulphur content: Not more than 10 ppb
(3) Smoke point: At least 30 mm (values above 35 mm and
even above 40 mm can be obtained)
(4) Density at 15°C: Not more than 0.77 g/m3
Provided that the extinguishing time according to
JIS 53031 is less than 125 seconds the extinguishing time
is shorter than that of a commercial kerosene and the
kerosene composition has a very high level of safety.
Furthermore, if the pour point is adjusted to not more
than -50°C then it can be handled easily even in cold
regions in winter.
The present invention will now be described in more
detail by reference to the following Examples:
Examples 1 and 2, Comparative Examples 1 to 3, Reference
Example 1
n-Paraffin/iso-paraffin mixed oils of the
._. 20 compositions shown in Table 1 were obtained by production
with SMDS {Shell Middle Distillate Synthesis) where
natural gas is partially oxidised and heavy paraffins are
synthesised by means of a Fischer-Tropsch synthesis and
the heavy paraffin oil obtained is subjected to
hydrocracking and distillation, and naphtha, kerosene and
light oil fractions are obtained.
The properties of the kerosene compositions of
Examples 1 and 2 and Comparative Examples 1 to 3 produced
by means of the SMDS process as described above and of a
general commercial JIS No.1 kerosene (Reference Example
1) are shown in Table 1.
CA 02549922 2006-06-15
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x
w
0 0 00 0 0 00 ~ 00 0 0
~. ~~ ,n
O ~N O l0~ l0~-iCDN I'~r-t~ OofM l9O M
-k ~ ~ ~ ~ ~~ ~ ~ ~p O r-Ir-iN c'7M I
U I IO Oc-I /~ ~-1~-Ic-i~-1~-I~-1r-1N N NN N NI V
M
W N O o O~.tm.cm.mn~ ~n~ntt~O ~
n
OM
O p~ M O l0V~N 61ODt~OJOV'd M~ M
N O a W c7 tnt~t~OD6161Or1N d'tnl0I~I 1
I~i I Il ~
l
r r Ov-I V I N r10-1r1v-1c-iv-iNN N NN N NV V
3C
W
~ O OO ~ O tnO O OO O O
1~in O ~-~7
L~O O 6lt-IlflM O 01t~l0Wit'w-1ODN 00L(~(''~
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U M l0O ON I l0/\ (-Io-I,-1,--fN N NN N NN N NV V
N
N
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~-
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The tests indicated below were carried out using the
kerosenes of the Examples, Comparative Examples and the
Reference Example.
Stove Combustion Test
The extinguishing time (JIS 53031), the amount of
heat generated (aircraft fuel oil A method, JIS K2279)
and the fuel consumption were measured using a wick type
convection stove (Model SZ-221, manufactured by Moto
Corona).
Method of Evaluating Combustion Performance
(1) Extinguishing Time (Normal Ignition)
Measurement of the extinguishing time was carried
out in accordance with JIS 53031. The fuel for
evaluation was burned for 1 hour with the wick in the
uppermost position and then the time taken for the flame
to be extinguished completely on visual observation when
the wick was lowered was taken to be the extinguishing
time. Evaluation of the extinguishing time was carried
out twice for each fuel. Moreover, the tests were
carried out in a dark room so that the flame could be
seen distinctly.
The evaluation was carried out following the
procedure indicated below.
(a) The fuel which was to be evaluated was
introduced into an empty stove accessory tank
and the fuel which had been left inside the
stove was removed with a syringe.
(b) The tank containing the fuel which was to be
evaluated was set in the stove.
(c) The fuel was burned for 1 hour with the wick in
the uppermost position.
(d) After burning for 1 hour, the wick was turned
down in one movement and extinguished.
(e) The time from when the wick had been turned
right down until the flame was seen visually to
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be completely extinguished was measured using a
stopwatch and recorded.
(f) The stove was re-lit and, after burning for 15
minutes, the extinguishing time was measured a
second time.
The results obtained are shown in Table 2.
(2) Fuel Consumption Test
This was carried out in the way summarised below.
(a) After removing any fuel remaining in the stove,
the fuel which was to be evaluated was
introduced.
(b) The stove as a whole was weighed.
(c) After burning the fuel which was to be
evaluated for 7 hours at the maximum combustion
for each stove, the stove was extinguished.
(d) After being extinguished, the whole of the
stove was weighed and the weight was recorded
and the fuel consumption was obtained from the
difference between the weight before the test
and the weight after the test.
The results obtained are shown in Table 3.
CA 02549922 2006-06-15
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x x
w w
~o
io a~ M
uWn o ~ ~r
O ~'M ~t' O N
U v--Ir-Iv-1 U o M r-iO1
M M
x x
W W t~
o t~ ,--a
4-t~ ~o t~ 4-mr
O M H N O ~I'~H
pC,,-1r-1v-1 fliO M r1 O
.-I r1
x x
W W
I~ N 01
M
O l007 N O ~' N dl
U W tt~l0 U O M c-I
N N
N N
H
Q'
N l~ M
~1'
x ~Ioo ~ x M
W t'~t~ t~ W O M v-1r-I
N N
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r-1 H
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I x aoo ~ x M
W OOOD of W O M ~-1l0
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U -1.-1c-I U O M v-I[-1
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t W t~1 4-I P +~ O ~-i
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'~ ~ ~-I .1-~~ ~I ~
F'. ~' t~'~-I
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w ~~'~ ~a ~~ ~~ a
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a ,
.
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As is clear from the Tables, the properties of the
kerosene compositions of the present invention are
excellent with a high smoke point of at least 30 mm, a
short extinguishing time and an excellent heating
capacity (amount of heat generated).
